The coordination of alkali–metal nickelates to organic π-systems: synthetic, structural and spectroscopic insights
Andryj M. Borys, Luca Vedani, Eva Hevia
Abstract
-CDT ligand enables facile ligand exchange with an assorted series of organic π-acceptors, ranging from polyaromatic hydrocarbons to ketones, imines and nitriles. For anthracene and phenanthrene, a homologous series of Li, Na and K nickelates could be obtained, which lead to different structural motifs or degrees of aggregation in the solid-state spanning solvated monomers to complex polymeric arrangements. For π-extended systems such as perylene or coronene, competing single-electron-transfer to give the corresponding radical anions was observed, illustrating the highly reducing nature of the alkali-metal nickelates. X-ray crystallographic analysis and NMR spectroscopy of the phenyl-alkali-metal nickelates reveal extreme back-bonding from Ni(0) to the organic π-acceptors due to strong σ-donation from the carbanionic ligands.